Dye transfer inhibiting compositions containing a metallocatalyst, a bleach and polyamine N-oxide polymer

ABSTRACT

A) A metallocatalyst selected from: a) metalloporphin and water-soluble or water-dispersable derivatives thereof; b) metaloporphyrin and water-soluble or water-dispersable derivatives thereof; c) metallophthalocyanine and water-soluble or water-dispersable derivatives thereof; B) a polyamine N-oxide containing polymers; C) an efficient amount of a bleaching agent.

FIELD OF THE INVENTION

The present invention relates to a composition and a process forinhibiting dye transfer between fabrics during washing.

BACKGROUND OF THE INVENTION

One of the most persistent and troublesome problems arising duringmodern fabric laundering operations is the tendency of some coloredfabrics to release dye into the laundering solutions. The dye is thentransferred onto other fabrics being washed therewith.

One way of overcoming this problem would be to complex or adsorb thefugitive dyes washed out of dyed fabrics before they have theopportunity to become attached to other articles in the wash.

Polymers have been used within detergent compositions to inhibit dyetransfer, such as disclosed in EP-A-102 923, DE-A-2 814 329, FR-A-2 144721 and EP-265 257.

Copending EP Patent Application 92202168.8 describes dye transferinhibiting compositions comprising polyamine N-oxides containingpolymers.

Another way of overcoming the problem of dye transfer would be to bleachthe fugitive dyes washed out of dyed fabrics before they have theopportunity to become attached to other articles in the wash.

Suspended or solubilized dyes can to some degree be oxidized in solutionby employing known bleaching agents.

GB 2 101 167 describes a stable liquid bleaching composition containinga hydrogen peroxide precursor which is activated to yield hydrogenperoxide on dilution.

However it is important at the same time not to bleach the dyes actuallyremaining on the fabrics, that is, not to cause color damage.

U.S. Patent 4,077,768 describes a process for inhibiting dye transfer bythe use of an oxidizing bleaching agent together with a catalyticcompound such as iron porphins.

Copending EP Patent Application 91202655.6 filed October 9, 1991,relates to dye transfer inhibiting compositions comprising an enzymaticsystem capable of generating hydrogen peroxide and porphin catalysts.

It has now been surprisingly found that polyamine N-oxide polymers andmetallo-catalysts provide superior and synergistic dye transferinhibiting properties compared to the catalyst- or polymers-system takenalone. This finding allows to formulate compositions which exhibitexcellent dye transfer inhibiting properties with low level ofcatalysts, which in turn, reduces the problem of catalyst depositiononto fabrics.

According to another embodiment of this invention a process is alsoprovided for laundering operations involving colored fabrics.

SUMMARY OF THE INVENTION

The present invention relates to inhibiting dye transfer compositionscomprising polyamine N-oxide containing polymers and metallo catalystsand an efficient amount of bleaching agent.

DETAILED DESCRIPTION OF THE INVENTION

Polyamine N-oxide Containing Polymers

The compositions of the present invention comprise as an essentialelement polyamine N-oxide polymers which contain units having thefollowing structure formula: ##STR1## herein P is a polymerisable unit,whereto the R--N--O group can be attached to or wherein the R--N--Ogroup forms part of the polymerisable unit or a combination of both.

A is ##STR2## x is or 0 or 1; R are aliphatic, ethoxylated aliphatics,aromatic, heterocyclic or alicyclic groups or any combination thereofwhereto the nitrogen of the N--O group can be attached or wherein thenitrogen of the N--O group is part of these groups.

The N--O group can be represented by the following general structures:##STR3## wherein R1, R2, R3 are aliphatic groups, aromatic, heterocyclicor alicyclic groups or combinations thereof, x or/and y or/and z is 0 or1 and wherein the nitrogen of the N--O group can be attached or whereinthe nitrogen of the N--O group forms part of these groups.

The N--O group can be part of the polymerisable unit (P) or can beattached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N--O group forms part of thepolymerisable unit comprise polyamine N-oxides wherein R is selectedfrom aliphatic, aromatic, alicyclic or heterocyclic groups.

One class of said polyamine N-oxides comprises the group of polyamineN-oxides wherein the nitrogen of the N--O group forms part of theR-group. Preferred polyamine N-oxides are those wherein R is aheterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine,piperidine and derivatives thereof.

Another class of said polyamine N-oxides comprises the group ofpolyamine N-oxides wherein the nitrogen of the N--O group is attached tothe R-group.

Other suitable polyamine N-oxides are the polyamineoxides whereto theN--O group is attached to the polymerisable unit. Preferred class ofthese polyamine N-oxides are the polyamine N-oxides having the generalformula (I) wherein R is an aromatic, heterocyclic or alicyclic groupswherein the nitrogen of the N--O functional group is part of said Rgroup.

Examples of these classes are polyamine oxides wherein R is aheterocyclic compound such as pyrridine, pyrrole, imidazole andderivatives thereof.

Another preferred class of polyamine N-oxides are the polyamine oxideshaving the general formula (I) wherein R are aromatic, heterocyclic oralicyclic groups wherein the nitrogen of the N--O functional group isattached to said R groups. Examples of these classes are polyamineoxides wherein R groups can be aromatic such as phenyl.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof.

The amine N-oxide polymers of the present invention typically have aratio of amine to the amine N-oxide of 10:1 to 1:1000000. However theamount of amine oxide groups present in the polyamine oxide polymer canbe varied by appropriate copolymerization or by appropriate degree ofN-oxidation. Preferably, the ratio of amine to amine N-oxide is from 3:1to 1:1000000. The polymers of the present invention actually encompassrandom or block copolymers where one monomer type is an amine N-oxideand the other monomer type is an N-oxide or not.

The amine oxide unit of the polyamine N-oxides has a pKa<10, preferablypKa<7, more preferred pKa<6.

The polyamine oxides can be obtained in almost any degree ofpolymerisation. The degree of polymerisation is not critical providedthe material has the desired water-solubility and dye-suspending power.

Typically, the average molecular weight is within the range of 500 to1000,000 ; more preferred 1000 to 500,000 ; most preferred 5000 to100,000.

The polyamine N-oxides of the present invention are typically presentfrom 0.01 to 10% , more preferably from 0.05 to 1%, most preferred from0.05 to 0.5% by weight of the dye transfer inhibiting composition.

Metallo Catalyst

The preferred usage range of the catalyst in the wash is 10⁻⁸ molar to10⁻³ molar, more preferred 10⁻⁶ -10⁻⁴ molar.

The essential metallo porphin structure may be visualized as indicatedin Formula I in the accompanying drawings. In Formula I the atompositions of the porphin structure are numbered conventionally and thedouble bonds are put in conventionally. In other formula, the doublebonds have been omitted in the drawings, but are actually present as inI.

Preferred metallo porphin structures are those substituted at one ormore of the 5, 10, 15 and 20 carbon positions of Formula I (Mesopositions), with a phenyl or pyridyl substituent selected from the groupconsisting of ##STR4## wherein n and m may be 0 or 1; A is selected fromwater-solubilizing group, e.g., sulfate, sulfonate, phosphate orcarboxylate groups; and B is selected from the group consisting of C₁-C₁₀ alkyl, C₁ -C₁₀ polyethoxy alkyl and C₁ -C₁₀ hydroxy alkyl.

Preferred molecules are those in which the substituents on the phenyl orpyridyl groups are* selected from the group consisting of --CH₃, --C₂H₅, --CH₂ CH₂ CH₂ SO₃ --, --CH₂ ----, and --CH₂ CH(OH)CH₂ SO₃ --, --SO₃.

A particularly preferred metallo phorphin is one in which the moleculeis substituted at the 5, 10 15, and 20 carbon positions with thesubstituent ##STR5##

This preferred compound is known as metallo tetrasulfonatedtetraphenylporphin. The symbol X¹ is (═CY--) wherein each Y,independently, is hydrogen, chlorine, bromine, fluorine or mesosubstituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl.

The symbol X² of Formula I represents an anion, preferably OH⁻⁻ or Cl⁻⁻.The compound of Formula I may be substituted at one or more of theremaining carbon positions with C₁ -C₁₀ alkyl, hydroxyalkyl or oxyalkylgroups. ##STR6##

Porphin derivatives also include chlorophyls, chlorines, i.e.isobacterio chlorines and bacteriochlorines.

Metallo porphyrin and water-soluble or water-dispersable derivativesthereof have a structure given in formula II. ##STR7## where X can bealkyl, alkyl carboxy, alkyl hydroxyl, vinyl, alkenyl, alkyl sulfate,alkylsulfonate, sulfate, sulfonate, aryl.

The symbol X² of Formula II represents an anion, preferably OH⁻⁻ orCl⁻⁻.

The symbol X can be alkyl, alkylcarboxy, alkylhydroxyl, vinyl, alkenyl,alkylsulfate, alkylsulfonate, sulfate, sulfonate.

Metallo phthalocyanine and derivatives have the structure indicated inFormula III, wherein the atom positions of the phthalocyanine structureare numbered conventionally. The anionic groups in the above structurescontain cations selected from the group consisting of sodium andpotassium cations or other non-interfering cations which leave thestructures water-soluble. Preferred phthalocyanine derivatives aremetallo phthalocyanine trisulfonate and metallo phthalocyaninetetrasulfonate. ##STR8##

Another form of substitution possible for the present invention issubstitution of the central metal by Fe, Mn, Co Rh, Cr, Ru, Mo or othertransition metals.

Still a number of considerations are significant in selecting variantsof or substituents in the basic porphin or azaporphin structure. In thefirst place, one would choose compounds which are available or can bereadily synthesized.

Beyond this, the choice of the substituent groups can be used to controlthe solubility of the catalyst in water or in detergent solutions. Yetagain, especially where it is desired to avoid attacking dyes attachedto solid surfaces, the substituents can control the affinity of thecatalyst compound for the surface. Thus, strongly negatively chargedsubstituted compounds, for instance the tetrasulfonated porphin, may berepelled by negatively charged stained surfaces and are therefore mostlikely not to cause attack on fixed dyes, whereas the cationic orzwitterionic compounds may be attracted to, or at least not repelled bysuch stained surfaces.

An Efficient Amount of Bleaching Agent

The dye transfer inhibiting compositions according to the presentinvention comprise an efficient amount of bleaching agent.

According to the present invention, an efficient amount of bleach is bydefinition the necessary amount of bleach which combined with a bleachcatalyst leads to a level of dye oxidation which is between 40% to 100%,preferably 40% to 60%, more preferred 60% to 80%, most preferred80%-100% of the maximum (Z) per cent of dye oxidation that can beachieved under the most optimal conditions determined by those skilledin the art.

The bleaches suitable for the present invention can be activated ornon-activated bleaches.

Preferably, the bleaches suitable for the present invention includeperoxygen bleaches. Examples of suitable water-soluble solid peroxygenbleaches include hydrogen peroxide releasing agents such as hydrogenperoxide, perborates, e.g. perborate monohydrate, perboratetetrahydrate, persulfates, percarbonates, peroxydisulfates,perphosphates and peroxyhydrates. Preferred bleaches are percarbonatesand perborates.

The hydrogen peroxide releasing agents can be used in combination withbleach activators such as tetraacetylethylenediamine (TAED),nonanoyloxybenzenesulfonate (NOBS, described in U.S. Pat. No.4,412,934),3,5,5-trimethylhexanoloxybenzenesulfonate (ISONOBS, describedin EP 120,591), or pentaacetylglucose (PAG), which are perhydrolyzed toform a peracid as the active bleaching species, leading to improvedbleaching effect.

The hydrogen peroxide may also be present by adding an enzymatic system(i.e. an enzyme and a substrate therefore) which is capable ofgenerating hydrogen peroxide at the beginning or during the washingand/or rinsing process. Such enzymatic systems are disclosed in EPPatent Application 91202655.6 filed Oct. 9, 1991.

Other peroxygen bleaches suitable for the present invention includeorganic peroxyacids such as percarboxylic acids.

TEST METHODS

For a given catalyst concentration, temperature and pH, the followingtwo test methods can be used to estimate the optimum bleach level thatgives the maximum level of dye oxidation, i.e. Z.

(a) In solution dye bleaching:

In a detergent solution, fix the initial concentration of dye (e.g. 40ppm) and catalyst. Record the absorbance spectrum of this solution usinga UV-V is spectrophotometer according to procedures known to thoseskilled in the art. Add a given concentration of bleach (H2O2, oxone,percarbonate, perborate, activated bleach, etc..) and stir the solutioncontaining the dye and catalyst. After stirring for 30 min, record againthe absorbance spectrum of the solution. The amount of dye oxidation canthen be determined from the change in the absorbance maximum for thedye. Keeping the experimental conditions the same, vary the amount ofbleach so as to achieve the maximum dye oxidation.

(b) Reduction of dye transfer from fabric to another fabric

In either a washing machine or launderometer, add a known bleedingfabric and a known uncolored pick-up tracer (e.g. cotton) to the washload. After simulating a wash cycle, determine the amount of dye thathas been picked up by the tracer according to methods known to thoseskilled in the art. Now to separate washing machines, add the sameamount of bleeding fabric and pick-up tracer, a fixed amount of catalystand vary the bleach level. Determine the level of dye transfer onto thepick-up tracers and vary the amount of bleach as to minimize dyetransfer. In this way the most optimal bleach concentration can bedetermined.

DETERGENT ADJUNCTS

A wide range of surfactants can be used in the detergent compositions. Atypical listing of anionic, nonionic, ampholytic and zwitterionicclasses, and species of these surfactants, is given in U.S. Pat. No.3,664,961 issued to Norris on May 23, 1972.

Mixtures of anionic surfactants are particularly suitable herein,especially mixtures of sulphonate and sulphate surfactants in a weightratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferablyfrom 3:1 to 1:1. Preferred sulphonates include alkyl benzene sulphonateshaving from 9 to 15, especially 11 to 13 carbon atoms in the alkylradical, and alpha-sulphonated methyl fatty acid esters in which thefatty acid is derived from a C₁₂ -C₁₈ fatty source preferably from a C₁₆-C₁₈ fatty source. In each instance the cation is an alkali metal,preferably sodium. Preferred sulphate surfactants are alkyl sulphateshaving from 12 to 18 carbon atoms in the alkyl radical, optionally inadmixture with ethoxy sulphates having from 10 to 20, preferably 10 to16 carbon atoms in the alkyl radical and an average degree ofethoxylation of 1 to 6. Examples of preferred alkyl sulphates herein aretallow alkyl sulphate, coconut alkyl sulphate, and C₁₄₋₁₅ alkylsulphates. The cation in each instance is again an alkali metal cation,preferably sodium.

One class of nonionic surfactants useful in the present invention arecondensates of ethylene oxide with a hydrophobic moiety to provide asurfactant having an average hydrophiliclipophilic balance (HLB) in therange from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10to 12.5. The hydrophobic (lipophilic) moiety may be aliphatic oraromatic in nature and the length of the polyoxyethylene group which iscondensed with any particular hydrophobic group can be readily adjustedto yield a water-soluble compound having the desired degree of balancebetween hydrophilic and hydrophobic elements.

Especially preferred nonionic surfactants of this type are the C₉ -C₁₅primary alcohol ethoxylates containing 3-8 moles of ethylene oxide permole of alcohol, particularly the C₁₄ -C₁₅ primary alcohols containing6-8 moles of ethylene oxide per mole of alcohol and the C₁₂ -C₁₄ primaryalcohols containing 3-5 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfactants comprises alkyl polyglucosidecompounds of general formula

    RO (C.sub.n H.sub.2n O).sub.t Z.sub.x

wherein Z is a moiety derived from glucose; R is a saturated hydrophobicalkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10and n is 2 or 3; x is from 1.3 to 4, the compounds including less than10% unreacted fatty alcohol and less than 50% short chain alkylpolyglucosides. Compounds of this type and their use in detergent aredisclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.

Also suitable as nonionic surfactants are poly hydroxy fatty acid amidesurfactants of the formula ##STR9## wherein R¹ is H, or R¹ is C₁₋₄hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R²is C₅₋₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linearhydrocarbyl chain with at least 3 hydroxyls directly connected to thechain, or an alkoxylated derivative thereof. Preferably, R¹ is methyl,R² is a straight C₁₁₋₁₅ alkyl or alkenyl chain such as coconut alkyl ormixtures thereof, and Z is derived from a reducing sugar such asglucose, fructose, maltose, lactose, in a reductive amination reaction.

The compositions according to the present invention may further comprisea builder system. Any conventional builder system is suitable for useherein including aluminosilicate materials, silicates, polycarboxylatesand fatty acids, materials such as ethylenediamine tetraacetate, metalion sequestrants such as aminopolyphosphonates, particularlyethylenediamine tetramethylene phosphonic acid and diethylene triaminepentamethylenephosphonic acid. Though less preferred for obviousenvironmental reasons, phosphate builders can also be used herein.

Suitable builders can be an inorganic ion exchange material, commonly aninorganic hydrated aluminosilicate material, more particularly ahydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.

Another suitable inorganic builder material is layered silicate, e.g.SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting ofsodium silicate (Na₂ Si₂ O₅).

Suitable polycarboxylates builders for use herein include citric acid,preferably in the form of a water-soluble salt, derivatives of succinicacid of the formula R--CH(COOH)CH2(COOH) wherein R is C10-20 alkyl oralkenyl, preferably C12-16, or wherein R can be substituted withhydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examplesinclude lauryl succinate , myristyl succinate, palmitylsuccinate2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinatebuilders are preferably used in the form of their water-soluble salts,including sodium, potassium, ammonium and alkanolammonium salts.

Other suitable polycarboxylates are oxodisuccinates and mixtures oftartrate monosuccinic and tartrate disuccinic acid such as described inU.S. Pat. No. 4,663,071.

Especially for the liquid execution herein, suitable fatty acid buildersfor use herein are saturated or unsaturated C10-18 fatty acids, as wellas well as the corresponding soaps.

Preferred saturated species have from 12 to 16 carbon atoms in the alkylchain. The preferred unsaturated fatty acid is oleic acid.

Preferred builder systems for use in granular compositions include amixture of a water-insoluble aluminosilicate builder such as zeolite A,and a watersoluble carboxylate chelating agent such as citric acid.

Other builder materials that can form part of the builder system for usein granular compositions the purposes of the invention include inorganicmaterials such as alkali metal carbonates, bicarbonates, silicates, andorganic materials such as the organic phosphonates, amiono polyalkylenephosphonates and amino polycarboxylates.

Other suitable water-soluble organic salts are the homo- or co-polymericacids or their salts, in which the polycarboxylic acid comprises atleast two carboxyl radicals separated from each other by not more thantwo carbon atoms.

Polymers of this type are disclosed in GB-A-1,596,756. Examples of suchsalts are polyacrylates of MW 2000-5000 and their copolymers with maleicanhydride, such copolymers having a molecular weight of from 20,000 to70,000, especially about 40,000.

Detergency builder salts are normally included in amounts of from 10% to80% by weight of the composition preferably from 20% to 70% and mostusually from 30% to 60% by weight.

Other components used in detergent compositions may be employed, such asbleaches, suds boosting or depressing agents, enzymes and stabilizers oractivators therefor, soil-suspending agents soil-release agents, opticalbrighteners, abrasives, bactericides, tarnish inhibitors, coloringagents, and perfumes.

Especially preferred are combinations with technologies which alsoprovide a type of color care benefit. Examples of these technologies arepolyvinylpyrrolidone polymers and other polymers which have dye transferinhibiting properties. Another example of said technologies arecellulase for color maintenance/rejuvenation.

Other examples are polymers disclosed in EP 92870017.8 filed Jan. 31,1992 and enzyme oxidation scavengers disclosed in EP 92870018.6 filedJan. 31, 1992. also particularly suitable are amine base catalyststabilizers disclosed in EP 92870019.4 filed Jan. 31, 1992.

The detergent compositions according to the invention can be in liquid,paste or granular forms. Granular compositions according to the presentinvention can also be in "compact form", i.e. they may have a relativelyhigher density than conventional granular detergents, i.e. from 550 to950 g/l; in such case, the granular detergent compositions according tothe present invention will contain a lower amount of "inorganic fillersalt", compared to conventional granular detergents; typical fillersalts are alkaline earth metal salts of sulphates and chlorides,typically sodium sulphate; "compact" detergents typically comprise notmore than 10% filler salt. The liquid compositions according to thepresent invention can also be in "compact form", in such case, theliquid detergent compositions according to the present invention willcontain a lower amount of water, compared to conventional liquiddetergents.

The present invention also relates to a process for inhibiting dyetransfer from one fabric to another of solubilized and suspended dyesencountered during fabric laundering operations involving coloredfabrics.

The process comprises contacting fabrics with a laundering solution ashereinbefore described.

The process of the invention is conveniently carried out in the courseof the washing process. The washing process is preferably carried out at5° C. to 75° C., especially 20 to 60, but the polymers are effective atup to 95° C. The pH of the treatment solution is preferably from 7 to11, especially from 7.5 to 10.5.

The process and compositions of the invention can also be used asadditive during laundry operations.

The following examples are meant to exemplify compositions of thepresent invention, but are not necessarily meant to limit or otherwisedefine the scope of the invention, said scope being determined accordingto claims which follow.

EXAMPLE I

The extent of dye transfer from different colored fabrics was studiedusing a launder-o-meter test which simulates a 30 min wash cycle. Thelaunder-o-meter beaker contains 200 ml of a detergent solution (pH7.5-10.5), a 10×10 cm piece of the colored fabric and a multi-fiberswatch which is used as a pick-up tracer for the bleeding dye. Themultifiber swatch consists of 6 strips (1.5 cm×1.5 cm each) made ofdifferent materials (polyacetate, cotton, polyamide, polyester, wool andorlon) which were sewn together.

The extent of dye transfer is reported in terms of the c value whichrepresents the change in the Hunter a, b values and is defined by thefollowing equation:

    ΔC={(a.sub.f a.sub.i).sup.2 +(b.sub.f -b.sub.i).sup.2 }.sup.1/2

where the subscripts i and f refer to the Hunter value before and afterwashing in the presence of the bleeding fabric, respectively.

EXAMPLE I(a) poly (4-vinylpyridine-N-oxide) and FeTPPS

The experimental conditions are:

A:detergent solution without any dye transfer inhibition system.

B:detergent solution containing 10 ppm of Iron-tetrasulfonatedphenylporphyrin (FeTPPS) and the optimum level of bleach as determinedfrom the test method above.

C:detergent solution containing 10 ppm ofpoly(4-vinylpyridine-N-oxide)(PVNO).

D:detergent solution containing 10 ppm of FeTPPS and 10 ppm ofpoly(4-vinylpyridine-N-oxide).

    ______________________________________                                                     Δ C value on cotton                                        Fabric         A      B         C    D                                        ______________________________________                                        blue sweater   15.2   14.7      8.2  4.8                                      purple trousers-1                                                                            19.3   7.0       17.8 2.8                                      green sweater  8.7    8.4       6.6  4.5                                      purple jogging 12.7   12.2      7.6  5.7                                      purple trousers                                                                              14.5   13.1      6.4  4.3                                      blue trousers  18.7   13.9      22.2 10.8                                     ______________________________________                                    

The higher the ΔC value, the more dye transferred onto the pick-upswatch.

Conclusion

The dye transfer inhibition benefits from the combined PVNO and FeTPPSare in all cases better than benefits provided by either the catalyst orpolymer alone. In addition, not only additive effects are observed butthese results show true synergism between the catalyst andpoly(4-vinylpyridine-N-oxide).

EXAMPLE I(b) poly (4 -vinylpyridine-N-oxide) and MnPc

The experimental conditions are:

A:detergent solution without any dye transfer inhibition system.

B:detergent solution containing 10 ppm of Mn-Phthalocyaninetetrasulfonated (MnPC) and the optimum level of bleach as determinedfrom the test method above.

C:detergent solution containing 10 ppm of poly(4-vinylpyridine-N-oxide).(PVNO)

D:detergent solution containing 10 ppm of MnPc and 10 ppm ofpoly(4-vinylpyridine-N-oxide).

    ______________________________________                                                    Δ C values on cotton                                        Fabric        A      B          C   D                                         ______________________________________                                        blue sweater  15.2   14.7       8.2 4.8                                       green sweater 8.7    8.4        6.6 4.5                                       purple jogging                                                                              12.7   12.2       7.6 5.7                                       purple trousers                                                                             14.5   13.1       6.4 4.3                                       ______________________________________                                    

Conclusion

The dye transfer inhibition benefits from the combined PVNO and MnPC arein all cases better than benefits provided by either the catalyst orpolymer alone. In addition, these results show true synergism betweenthe catalyst and poly(4-vinylpyridine-N-oxide).

EXAMPLE II (A/B/C/D)

A liquid dye transfer inhibiting composition according to the presentinvention is prepared, having the following compositions:

    ______________________________________                                        Linear alkyl benzene sulfonate                                                                       10                                                     Sodium C.sub.12-15 alkyl sulfate                                                                     3                                                      C.sub.14-15 alkyl 2.5 times ethoxylated sulfate                                                      0                                                      C.sub.12 glucose amide 0                                                      C.sub.12-15 alcohol 7 times ethoxylated                                                              11.6                                                   Oleic acid             2.5                                                    Citric acid            1                                                      C.sub.12-14 alkenyl substituted succinic acid                                                        0                                                      Sodium Hydroxide       3.5                                                    Ethanol                6                                                      Monoethanolamine       0                                                      Triethanolamine        6.4                                                    1,2-propane diol       1.5                                                    Glycerol               0                                                      Boric acid             0                                                      Diethylene triamine penta                                                                            0.8                                                    (methylene phosphonic acid)                                                   CaCl.sub.2             0                                                      Soil release polymers  0.5                                                    Fatty acids            12                                                     Enzymes                0.65                                                   Water and minors       Balance to 100%                                        ______________________________________                                    

The above composition was supplemented with the catalyst, polymer andbleach according to table I

                  TABLE I                                                         ______________________________________                                                        A      B      C      D                                        ______________________________________                                        Catalyst 1: Mn-tetrasulfonated                                                                  0        0.05   0    0                                      tetraphenylporphine                                                           Catalyst 2: Cr-tetrasulfonated                                                                  0        0      0.100                                                                              0                                      tetraphenylporphine                                                           Catalyst 3: Fe tetrasulfonated                                                                  0        0      0    0.2                                    tetraphenylporphine                                                           Catalyst 4: Mn-Phthalocyanine                                                                   0.15     0.0    0    0                                      tetrasulfonated                                                               H.sub.2 O.sub.2   0.3-0.5  0      0    0                                      Perborate         0        0      1-5  0.5                                    Percarbonate      0        0.4    0    0.100-                                 Poly(4-vinylpyridine-N-oxide)                                                                   0.1      0.3    0.05 0.2                                    TAED              0        0      0.5  0                                      ______________________________________                                    

EXAMPLE III (A/B/C/D)

A compact granular dye transfer inhibiting composition according to thepresent invention is prepared, having the following formulation:

    ______________________________________                                                             %                                                        ______________________________________                                        Linear alkyl benzene sulphonate                                                                      11.40                                                  Tallow alkyl sulphate  1.80                                                   C.sub.45 alkyl sulphate                                                                              3.00                                                   C.sub.45 alcohol 7 times ethoxylated                                                                 4.00                                                   Tallow alcohol 11 times ethoxylated                                                                  1.80                                                   Dispersant             0.07                                                   Silicone fluid         0.80                                                   Trisodium citrate      14.00                                                  Citric acid            3.00                                                   Zeolite                32.50                                                  Maleic acid actylic acid copolymer                                                                   5.00                                                   DETMPA                 1.00                                                   Cellulase (active protein)                                                                           0.03                                                   Alkalase/BAN           0.60                                                   Lipase                 0.36                                                   Sodium silicate        2.00                                                   Sodium sulphate        3.50                                                   Minors                 up to 100                                              ______________________________________                                    

The above composition was supplemented with the catalyst, polymer andbleach according to table II

                  TABLE II                                                        ______________________________________                                                       A     B      C        D                                        ______________________________________                                        Catalyst 1: Mn-tetrasulfonated                                                                 0       0.05   0      0                                      tetraphenylporphine                                                           Catalyst 2: Cr-tetrasulfonated                                                                 0       0      0.100  0                                      tetraphenylporphine                                                           Catalyst 3: Fe-tetrasulfonated                                                                 0       0      0      0.2                                    tetraphenylporphine                                                           Catalyst 4: Mn-Phthalocyanine                                                                  0.15    0.0    0      0                                      tetrasulfonated                                                               H.sub.2 O.sub.2  0.3-0.5 0      0      0                                      Perborate        0       0      1-5    2.5                                    Percarbonate     0       0.4    0      0                                      Poly(4-vinylpyridine-N-oxide)                                                                  0.05    0.1    0.15   0.2-0.4                                TAED             0       0      0.5    1.0                                    ______________________________________                                    

We claim:
 1. A dye transfer inhibiting composition comprising:A. ametallo catalyst selected froma) metallo porphin and water-soluble orwater-dispersable derivatives thereof, b) metallo porphyrin andwater-soluble or water-dispersable derivatives thereof, c) metallophthalocyanine and water-soluble or water-dispersable derivativesthereof, wherein the wash concentration of metallo catalyst is from 10⁻⁸to 10⁻³ molar, B. from 0.01% to 10% of polyamine N-oxide containingpolymers having a ratio of amine to amine N-oxide of 10:1 to1:1,000,000. and an average molecular weight within the range of 500 to1,000,000; C. an efficient mount of a bleaching agent which, combinedwith the metallo catalyst, leads to a level of dye oxidation between 40%to 100% of maximum dye oxidation.
 2. A dye transfer inhibitingcomposition according to claim 1 containing a metallo porphinderivative, wherein said porphin is substituted on at least one of itsmeso positions with a phenyl or pyridyl substituent selected from thegroup consisting of ##STR10## wherein n and m may be 0 or 1, A isselected from the water-solubilizing group, e.g., sulfate, sulfonate,phosphate, and carboxylate groups, and B is selected from the groupconsisting of C₁ -C₁₀ alkyl, C₁ -C₁₀ polyethoxyalkyl and C₁ -C₁₀hydroxyalkyl.
 3. A dye transfer inhibiting composition according toclaim 2 wherein the substituents on the phenyl or pyridyl groups areselected from the group consisting of --CH₃, --C₂ H₅, --CH₂ CH₂ CH₂ SO₃--, --CH₂ COO--, --CH₂ C--H(OH)CH₂ SO₃ --, and --SO₃.
 4. A dye transferinhibiting composition according to claim 1, containing a metalloporphin derivative, wherein said metallo porphin is substituted on atleast one of its meso positions with a phenyl substituent selected fromthe group consisting of ##STR11## wherein X¹ is (═CY--) wherein each Y,independently, is hydrogen, chlorine, bromine or meso substituted alkyl,cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl.
 5. A dye transferinhibiting composition according to claim 1 wherein the central atom isselected from Fe, Mn, Co, Rh, Cr, Ru, Mo or other transition metals. 6.A dye transfer inhibiting composition according to claim 1 wherein thewash concentration of metallo catalyst is from 10⁻⁸ to 10⁻³ molar,preferably from 10⁻⁶ to 10⁻⁴ molar.
 7. A dye transfer inhibitingcomposition according to claim 1 wherein the polyamine N-oxide ispolyvinylpyridine N-oxide.
 8. A dye transfer inhibiting compositionaccording to claim 1 wherein the bleaching agent is selected from anactivated or a non-activated bleach.
 9. A dye transfer inhibitingcomposition according to claim 1 which is a detergent additive, in theform of a non-dusting granule or a liquid.
 10. A detergent compositionwhich comprises an effective amount of a dye transfer inhibitingcomposition according to any of the preceding claims further comprisingeffective amounts of at least one of the following: enzymes,surfactants, and/or builders.
 11. A detergent composition whichcomprises a dye transfer inhibiting composition according to any of thepreceding claims further comprising a cellulase in an amount sufficientto enhance fabric color maintenance and/or rejuvenation.